Process for production of phenol and ketones by decomposition of hydroperoxides



Patented Dec. 22, 1953 PROCESS FOR PRODUCTION OF PHENOL AND KETONES BY DECOMPOSITION OF HYDROPEROXIDES Leo J. Filar and Milton A. Taves, Wilmington, Del.,'assignors to Hercules Powder Company, Wilmington, Del., a corporation of Delaware No Drawing. Application December 30, 1949,

Serial No. 136,162

11 Claims. (01. 260-593) This invention relates to a,a-dialkylarylmethyl hydroperoxides, and more particularly to a process for the conversion of these hydroperoxides to phenols and aliphatic ketones.

There have been numerous processes developed for the purpose of producing phenols synthetically due to the fact that the demand for phenols, such as the cresols and phenol itself, far exceeds the amount which may be recovered in the refining of coal tar. Only a limited number of the processes for the preparation of phenol have proved sufiiciently satisfactory to be applicable to commercial production. One of these involves the sulfonation of benzene and the formation of sodium benzene sulfonate which is fused with sodium hydroxide to produce sodium phenolate. yields phenol, which may be purified by distillation. However, probably the most widely used commercial process today for the preparation of phenol is that of hydrolyzing chlorobenzene with aqueous sodium hydroxide under conditions of high temperature and pressure to produce sodium phenolate, which then is acidified to give phenol. The chlorobenzene may be prepared either by direct chlorination of benzene or by chlorination with a mixture of hydrogen chloride and oxygen.

Even those processes which have been adapted to commercial production of phenol are not entirely satisfactory. They require large equipment investment and installation to provide facilities for the raw materials used, and they must be operated on the basis of large production capacity in order to produce phenol at a reasonable price. lin addition, the processes are disadvantageous because of the many steps involved and the considerable problem of disposal of waste waters contaminated with phenol.

Now in accordance with this invention it has been found that phenols and aliphatic ketones may be prepared simply, efliciently, economically, and simultaneously from a,a-dialkylarylmeth yl hydroperoxides by adding such a hydroperoxide to a homogeneous reaction medium comprising acetone and concentrated sulfuric acid, the concentration of the sulfuric acid in the reaction medium being from about 0.05 to about by weight. In addition to producing phenols, the process at the same time produces aliphatic ketones as valuable products. This also is in contrast to previous processes for preparing phenols.

As an example of carrying out the process in accordance with this invention, a,u-dimethylbenzyl hydroperoxide is gradually added to a solution of acetone and about 1% by weight of con- The phenolate upon acidificationcentrated sulfuric acid at a temperature of about C., the rate of addition being so controlled that the decomposition proceeds rapidly and there is no build-up in the solution of a high concentration of the hydroperoxide. Upon completion of the reaction, the sulfuric acid in the reaction mixture is neutralized and the mixture then distilled to recover phenol. In the case of a,a-dimethylbenzyl hydroperoxide, the other product of the decomposition reaction is acetone, and the total acetone also may be recovered by the distillation step.

The following examples constitute specific illustrations of the embodiments of the invention generally outlined above. All amounts are based on parts by weight.

Example 1 A reaction vessel equipped with a stirrer, an inlet for the hydroperoxide, a thermometer, and a reflux condenser was charged with 1 part of concentrated sulfuric acid dissolved in parts of acetone. The acid was commercial acid con taining -96% sulfuric acid and having a specific gravity of 1.84. The acetone solution was heated to reflux (56 0.), the source of heat was removed, and there then was added slowly 225 parts of a cumene oxidate containing 83.7% 11,1;- dimethylbenzyl hydroperoxide. The addition of the hydroperoxide resulted in a vigorous, spontaneous refluxing of the solvent, the rate of which was easily controlled by the rate of addition of the hydroperoxide. During the 30-minute addition time, the temperature of the reaction mixture slowly rose to a maximum of 76 C. Upon completion of the reaction, the mixture was allowed to stand for an additional 30 minutes, after which there was added 4 parts of sodium bicarbonate. The reaction mixture then was distilled using both atmospheric and reduced pressures. At a temperature of 55-55.8 C. under atmospheric pressure there was collected a fraction composed of 142.7 parts of acetone having a refractive index at 20 C. of 1.3598. The pressure then was reduced to 7 mm, and over a temperature range of 3470.5 C. there was collected a fraction composed of 20.8 parts and containing 4.8% phenol. The next fraction, collected at V 70.5-73.5 C. under a pressure of 7 8 mm., was composed of 110.5 parts of phenol assaying (U. S. P.) 99.1% phenol and 0.03% nonvolatiles. The distillation residue amounted to 18.1 parts, and there also was recovered from the distillation trap 7.5 parts of material. On the basis of this distillation the recovery of acetone was 97% of hydrop oxide w Example 2 Into the same apparatus described in Example, 1 was charged a solution composed of ()A part of concentrated sulfuric acid must ng of a solvent composed of 20% phenol and 80% acetone." ihis solution was heated to 60 C. and there then was added to the solution 18,5 parts of a cum enet oxidate containing 88.4% -a,al-dimethylbenzyl hydroperoxide. The addition" was. "carried out over a period of about 20 mir utesthe tep ture being maintained in theraifge offifl by means of external cooling. At the end time the hydroperoxide was complete1yidecom-' posed and the reaction mixture, after addition of H ui' a-l e 9L 599. 343 193211293 5 5 Je t QSP EQ re uc s e miter m te! of, he "Ens rst d is}; 393! *in'ountedto p the hasis qitttljiiq distillationlthefi li via can 'fie he t h at tak n tfiea'm u of phenol e fl t i e es V s unas hesol L t was 'com w s was duplicated ewe? 3- 1 5. j pon ects 'iu ,dc j e.

Theepparatus t describedl Example 1 was char ed Mith; aisolution v,of 10,15 part iof concentratedsulrfuric acidl-im52 parts of acetone; The solution was heated tdrefluxil 561C.) \andito this olution as cnadcled 18.5 parts or. a...py e oxidatec ntainine 5 ,2% ,wd methrl p=methy1- hepzizhhydroperpxide The addition, was. cara ss nt ll omnlet l di tom: w field ithes asti mix we neutra ized b t aediti ao ab ut 1o .3-par L cad ceu sesiiimiz ydr i si ndah mix: ii l a wess isti eh o e t asnv s 1 At. agtemserae 5 mice t5 i E ture of 8l-96 C. under a pressure of 16 mm. there was collected a fraction of 6.9 parts containing 44% p-creso1. The next fraction was collected at e5-97.5 C. under a pressure of 15-16 min and amounted toil-parts containing 97% Ilrfll'ESQl. The final fraction was collected at a temperature of -l20 C. under a pressure of iii-15 mm. It amounted to 18.? parts containing 6 2% p-ci esol, 'Ijhe yield of p-cresol was 82.6%

hased on this distillation.

Example 5 mechanical stirrer; a condenser, an inlet for introduction of the hydroperoxide, an inlet for mtroduction of the sulfuric acid-acetone solution, and an outlet placed ahout one-third of the disassespa eams 2 t e a iens ia j mp fi Q, some onir -tim mi tum a he be i nin qfh op a i a hs s n vessel wasfcharged w ith. a solution composedol ass pneendl 4 53?- zj ie a n ce o of. 0noentrainedsulfuric acid. a-Dimethyloenzjyl hydroperoxide then was t. introduced into he ca 'ssslf a l-l h s v li th ction mixture s above that or the outlet. At. this time; the reaction mixture'was allowed to flow from the vesselandfacetonewas recqvered from the condenser, blended with additional sulfuric acid and. fed back t0,the1 reaction mixture, These, individual operations, were. so adjusted that the recycled acetone containing make-Yup acid wa'sintroduced at the samerate as ac tqne waslrecovered fr m thecondenser. Themak eeup acid was introd d at the rate of 1%, basedon he y r e exi c e d andtne. e iQntprodllQb w s. emeved at he: ame at v s he hydroperoxide was introduced. By this procedurethere w s. .des m c sd z fitl g rts ia nmm t xidate a ni til-5%,. ie rdimct nzyi. hydro? peroxide. "The oxidate was introduced at atrate of 17.2,parts per minute, Duringthe reaction the tempe atu ffl ii v rc was 905 ca e e t rs im 1 he h o croxidc: wa s n es and he. i i snt reaction ro duct cona gi, 0- 1 he. y ro er x da. U pndist lation of the product, there wa IQCQYGI'QQJQH) pan of 1i d ph ql. Th s mircsuonded to, a Yield fib n hich 4 6 v if htthemeticalI ei fi 1 3- iesss v f ihis ny a qnh sb en Set fbith the asap-nit s p liedt heh dro: i i s, aisedilsm th oxid tio f xceue i isna other w-d a lar lm tn l h dro: PemXiliS 31$? we .v fi ble-u u h th diiope ox dcs may be prepared b y the oxidatign or" alizyl-sub: t aromati pr nicpcm ounds ha ing-the i ucm iermula in ,which R1. and R2-= represent*alky1 groupsand Ar represents a .substituent selected fromthe group consisting of aryl and alkarylgroups; The oxidation may be carried out in the liquid phase utilizing anor molecular oxygen as the oxidizing agents. One method ,of preparing these hydroperoxides involves the liquid .phase oxidation of the-alkyl-substituted aromatic organic compounds at a temperature betweenabout 25 C; and about.

95 C. in the presence of an aqueous alkali. The concentration of the aqueous alkali may be between about 0.01 and about 35%, although it is preferable to use concentrations of about 0.01 to about 2%. Vigorous agitation is desirable during the oxidation reaction. A preferred method of preparing the hydroperoxides, however, involves intimately contacting under anhydrous, noncatalytic conditions the alkyl-substituted aromatic organic compound in liquid phase with an oxygen-containing gas, such as air or molecular oxygen, in the presence of a peroxidic free radical oxidation initiator, such as an organic peroxide, hydroperoxide or compound capable of decomposing to form organic free radicals. In contrast to the method first discussed, the latter oxidation is carried out in the absence of an aqueous phase, and there is obtained a substantially anhydrous reaction product which is one of the more preferable hydroperoxide materials to use in the process of this invention.

The can dialkylarylmethyl hydroperoxides which may be used in accordance with the process of this invention have the following structural formula R1 OOH Ra Ar in which R1 and R2 represent alkyl groups, Ar represents a substituent selected from the group consisting of aryl and alkaryl groups, and the OOH group represents a hydroperoxy group. As illustrative of the alkyl-substituted aromatic organic compounds which may be oxidized, p-cymene, cumene, diisopropylben zene, sec-butylbenzene, p-ethylisopropylbenzene, and isopropylnaphthalene may be mentioned. These compounds lead to a,a-dimethyl-p-methylbenzyl, a,a. dimethylbenzyl, m dimethyl-p-isopropylbenzyl, a,a ethylmethylbenzyl, 11,0. dimethyl p ethylbenzyl, and c,a-dimethylnaphthylmethyl hydroperoxides, respectively. Also, in the case of diisopropylbenzene and p-ethylisopropylbenzene it is possible to obtain dihydroperoxides. For example, a,a,a.',c-tetramethyl p xylene dihydroperoxide may be obtained from p-diisopropylbenzene. These compounds also may be named as aryl- (dialkybmethyl hydroperoxides; for example, a,a-dimethylbenzyl hydroperoxide may be designated as phenyl(dimethyl) methyl hydroperoxide. The aryl and alkaryl groups need not be derived from benzene, as is the case in most of the aforementioned compounds, for compounds containing aromatic nuclei derived from naphthalene, anthracene, phenanthrene, and the like also are operable when dissolved in a suitable solvent during the oxidation. The aryl group may be substituted with alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, and the like to give alkaryl substituents, the same alkyl groups also being representative of R1 and R2 in the structural formula. R1 and R2 may be either the same or different. The oxidation of the alkyl-substituted aromatic organic compounds may be carried out upon the compounds themselves if they are liquids or upon solutions of the compounds if the latter are solids at the oxidation temperature.

In carrying out the decomposition process of this invention, several different modifications of the a,a-dialkylarylmethyl hydroperoxides may be used. The hydroperoxide may be utilized, for example, either in the form of the pure hydroperoxide or in the form of a crude oxidation reaction mixture containingi'the" hydroperoxide. When the hydroperoxide is obtained by molecular oxygen oxidation, the oxidation usually is interrupted before all of the hydrocarbon has reacted in order to avoid or limit side reactions. The a,a-dialkylarylmethyl hydroperoxide then is obtained in mixture with smaller or larger amounts of the original hydrocarbon, which is an amt-dialkylarylmethane, and the mixture also may contain small amounts of secondary reaction products such as the corresponding alcohols, which are a,a-dialkylarylmethyl alcohols. The oxidation of cumene, for example, leads to a reaction prodnot containing a,a-dimethylbenzyl hydroperoxide, unchanged cumene and small amounts of a,a-di' methylbenzyl alcohol and acetophenone. However, by the preferred method of oxidation described previously the hydroperoxide may be obtained to the virtual exclusion of the alcohol and ketone secondary reaction products. Such reaction products may be used per se in the process of this invention.

It is preferable, however, to utilize the hydroperoxide in a more concentrated form, and a concentrate of the hydroperoxide may be obtained by separating the other constituents of the crude oxidation reaction mixture. The hydroperoxides may be separated from the oxidation reaction mixtures by, for example, fractional distillation at very low pressures, of the order of 0.01 to 1.0 mm. of mercury, the hydroperoxides having higher boiling points than the related hydrocarbon, alcohol and ketone." In some instances the hydroperoxides also maybe separated from the oxidation reaction mixtures by crystal lization, which may be facilitated by first distilling off at least part of the hydrocarbon. An-

other method of separating the hydroperoxides from the oxidation reaction mixture involves precipitation of the hydroperoxide with a concen-- trated aqueous solution (25 to 40%) of sodium hydroxide. The precipitate is crystalline. The precipitate of a,a-dimethy1benzyl hydroperoxide, for example, analyzes for the sodium salt of the hydroperoxide associated with four molecules of water. V

The decomposition of the hydroperoxides in accordance with the process of this invention is carried out in a homogeneous reaction medium comprising acetone and between about 0.05 and about 10% 'by weight of concentrated sulfuric acid based on the reaction medium. The reaction medium must be homogeneous not only initially, but also throughout the reaction, in order to obtain the advantages of the process, for example, permissibility of using low concentrations of the concentrated sulfuric acid catalyst, and highly eflicient contact between the catalyst and the hydroperoxide. The use of acetone in the reaction medium also is advantageous in that this low-boiling solvent dissipates most of the considerable heat of reaction through reflux. Fur thermore, since the solvent of the reaction medium is generally composed of one or more of the decomposition reaction products, there is no cornplication from the presence of appreciable amounts of a foreign material in the separation and purification of the products.

The reaction medium should not contain too much water since the presence of considerable amounts of water will render the medium heterogeneous. The reaction medium soon after reaction has begun will contain acetone, the phenol corresponding to the hydroperoxide being decomposed, and some of the hydroperoxide itself.

phenol-contaminated waste water, since the presence of phenol in water generally is undesirable, as when the water later may be utilized for drinking purposes' The advantages of the present process, particularly in so far as elimination of the presence of phenol-contaminated waste water is concerned, may be better seen from the overall standpoint of converting benzene to phenol. One of the overall processes involved in this invention comprises the alirylation of benzene with propylene to obtain cumene, oxidation of the cumene under anhydrous conditions and in the absence of catalysts to obtain a,a-dimethylbenzyl hydroperoxide, decomposition of this hydroperoxide in accordance with the process of this invention to give phenol and acetone as products, and separation of the phenol and acetone from the reaction mixture. In none of the steps involving the oxidation and decomposition is it necessary to have water present, consequently, the problem of disposing phenol-contaminated waste water is eliminated. A further advantage of the overall process is that the combination of the oxidation and decomposition steps may be made continuous. Theoxidation, for example, may be carried out in one reactor, the oxidation reaction mixture distilled to obtain a concentrated hydroperoxide, and the concentrated hydroperoxide then transferred directly to the reactor in which the decomposition reaction is effected.

The process in accordance with this invention represents a more economical and efiicient means for obtaining not only phenol itself but also other phenolic compounds such as p-cresol and hydroquinone. The latter two compounds are, of course, obtained by the decomposition of 1 dimethyl p methylbenzyl hydroperoxide and o.,0.-tetramethyl-p-xylylene dihydroperoxide, respectively. Due to the simple nature of the process, the latter will be found particularly applicable to small scale installations and will not require the vast outlay of capital and equipment required by previous processes.

What We claim and desire to protect by Letters Patentis:

1. The process of producing a phenol and an aliphatic ketone by decomposition of an mil-dialkylarylmethyl hydroperoxide which comprises adding said hydroperoxide to a homogeneous reaction medium comprising acetone and concentrated sulfuric acid, the concentration of said acid in said medium being between about 0.05 and about 10% by weight and any water present being in an amount less than that required to render the reaction medium heterogeneous.

2. The process of producing a phenol and an aliphatic ketone by decomposition of an a t-dialkylarylmethyl hydroperoxide which comprises adding said hydroperoxide to a homogeneous reaction medium comprising acetone and concentrated sulfuric acid, the concentration of said acid in said medium being between about 0.1 and about 2% by weight and any water present being in an amount less than that required to render the reaction medium heterogeneous.

3. The process of producing a phenol and an aliphatic ketone by decomposition of an a,a-dialkylarylmethyl hydroperoxide which comprises adding said hydroperoxide to a homogeneous reaction medium comprising acetone and concentrated sulfuric acid at a temperature between about and about 100 0., the concentration of said acid in said medium being between about 0.05 and about by weight and any water 10 present" being in an amount less than that required to render the reaction medium heterogeneous.

4. The process of producing a phenol and an aliphatic ketone by decomposition of an amt-CH- alkylarylmethyl hydroperoxide which comprises adding said hydroperoxide to a homogeneous reaction medium comprising acetone and concentrated sulfuric acid at a temperature between about 30 and about C., the concentration of said acid in said medium being between about 0.05 and about"l0% by weight and'any water present being. in an amount less than that re-' quired to render the reaction medium heterogeneous.

5. The process of producing a phenol and an aliphatic ketone by decomposition of an mot-dialkylarylmethyl hydroperoxide which comprises adding said hydroperoxide to a homogeneous reaction medium comprising acetone and concentrated sulfuric acid, the concentration of said acid in said medium being between about 0.05 and about 10% by weight and any water present being in an amount less than that required to render the reaction medium heterogeneous, and separating a phenol and an aliphatic ketone from the reaction mixture.

6. The process of producing phenol and acetone by decomposition of a,a-dimethylbenzyl hydroperoxide which comprises addin said hydroperoxide to a homogeneous reaction medium comprising acetone and concentrated sulfuric acid, the concentration of said acid in said medium being between about 0.05 and about 10% by weight and any water present being in an amount less than that required to render the reaction medium heterogeneous.

7. The process of producing phenol and acetone by decomposition of a,a-dimethylbenzyl hydroperoxide which comprises adding said hydroperoxide to a homogeneous reaction medium comprising acetone and concentrated sulfuric acid at a temperature between about 30 and about 90 C., the concentration of said acid in said medium being between about 0.1 and about 2% by weight and any water present being in an amount less than that required to render the reaction medium heterogeneous, and separating phenol and. acetone from the reaction mixture.

8. The process of producing p-cresol and. acetone by decomposition of a,a-dimethyl-p-methylbenzyl hydroperoxide which comprises adding said hydroperoxide to a homogeneous reaction medium comprising acetone and concentrated sulfuric acid, the concentration of said acid in said medium being between about 0.05 and about 10% by weight and any water present being in an amount less than that required to render the reaction medium heterogeneous.

9. The process of producing hydroquinone and acetone by decomposition of a,a,a',a-tetramethylp-xylylene dihydroperoxide which comprises adding said dihydroperoxide to a homogeneous reaction medium comprising acetone and concentrated sulfuric acid, the concentration of said acid in said medium being between about 0.05 and about 10% by weight and any water present being in an amount less than that required to render the reaction medium heterogeneous.

10. The process of producing a phenol and an aliphatic ketone by decomposition of an a,a-d1- alkylarylmethyl hydroperoxide which comprises adding said hydroperoxide to a homogeneous reaction medium comprising acetone, a phenol and concentrated sulfuric acid, the concentration of comprising acetone, phenol and concentrated 5 11- 1 furic .acid', the concentration .ofsaid acid in said medium being between about 0:05 and about 110% by weight and any water present being in amount iess than that required tori-sander the reaction mediumheterogeneons.

LEO .J. MILTON A. TAVES.

References Gited in the file of this patent FOREIGN PATENTS Country Date GreatBxitain ,V Sept. 20, 1949 OTHER REFERENCES Hock et aL. Berichte, v01. 7'7, pages 257-264 (1944).

Number 

1. THE PROCESS OF PRODUCING A PHENOL AND AN ALIPHATIC KETONE BY DECOMPOSITION OF AN A,A-DIALKYLARYLMETHYL HYDROPEROXIDE WHICH COMPRISES ADDING SAID HYDROPEROXIDE TO A HOMOGENEOUS REACTION MEDIUM COMPRISING ACETONE AND CONCENTRATED SULFURIC ACID, THE CONCENTRATION OF SAID ACID IN SAID MEDIUM BEING BETWEEN ABOUYT 0.05 AND ABOUT 10% BY WEIGHT AND ANY WATER PRESENT BEING IN AN AMOUNT LESS THAN THAT REQUIRED TO RENDER THE REACTION MEDIUM HETEROGENEOUS. 